CN105047904A - Preparation method and application of titanium-cobalt spinel - Google Patents
Preparation method and application of titanium-cobalt spinel Download PDFInfo
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- CN105047904A CN105047904A CN201510336564.7A CN201510336564A CN105047904A CN 105047904 A CN105047904 A CN 105047904A CN 201510336564 A CN201510336564 A CN 201510336564A CN 105047904 A CN105047904 A CN 105047904A
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- titanium
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- cobalt spinel
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 51
- 239000011029 spinel Substances 0.000 title claims abstract description 51
- NNSIWZRTNZEWMS-UHFFFAOYSA-N cobalt titanium Chemical compound [Ti].[Co] NNSIWZRTNZEWMS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 39
- 239000010936 titanium Substances 0.000 claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 239000002086 nanomaterial Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000002671 adjuvant Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- GDUDPOLSCZNKMK-UHFFFAOYSA-L cobalt(2+);diacetate;hydrate Chemical compound O.[Co+2].CC([O-])=O.CC([O-])=O GDUDPOLSCZNKMK-UHFFFAOYSA-L 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- HFDCVHDLKUZMDI-UHFFFAOYSA-N sulfuric acid titanium Chemical compound [Ti].OS(O)(=O)=O HFDCVHDLKUZMDI-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 235000011837 pasties Nutrition 0.000 claims description 4
- 238000011056 performance test Methods 0.000 claims description 4
- 229930091371 Fructose Natural products 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- OAILYZSOYSCLLE-UHFFFAOYSA-N cobalt oxalic acid hydrate Chemical compound O.C(C(=O)O)(=O)O.[Co] OAILYZSOYSCLLE-UHFFFAOYSA-N 0.000 claims description 3
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 150000001720 carbohydrates Chemical class 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract 5
- 239000000654 additive Substances 0.000 abstract 3
- 230000000996 additive effect Effects 0.000 abstract 3
- 239000007773 negative electrode material Substances 0.000 abstract 3
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 230000005260 alpha ray Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A preparation method and application of titanium-cobalt spinel belongs to preparation methods and applications of transition-metal spinel, and specifically is a preparation method for a titanium-cobalt spinel (Co2TiO4) octahedral-nanostructure material and an application of the titanium-cobalt spinel (Co2TiO4) octahedral-nanostructure material to a negative electrode material of a lithium ion battery. A mild liquid phase synthesis technique is utilized to prepare a cobalt titanate nanostructure, and parameters in a reaction process are adjusted and controlled, so that the titanium-cobalt spinel octahedral-nanostructure material is compounded conveniently in low cost and is applied as the negative electrode material of the lithium ion battery. The preparation method comprises the steps of: respectively preparing solutions by utilizing a titanium source and a cobalt source, mixing the prepared solutions according to a molar ratio of (1-5) : 1, stirring the mixed solution uniformly, and putting the uniformly stirred solution in a closed pressure-resistant vessel to react for 8-40 hours at 100-250 DEG C, wherein an alkali additive is added to the titanium-source preparation solution, and a saccharide additive and an amine additive are added to the cobalt-source preparation solution. According to the preparation method, the raw materials are easy to obtain, a synthesis method is simple, and the controllability of operation steps is high; the obtained titanium-cobalt spinel has high purity and uniform particle size, and expanded production is easy. If the titanium-cobalt spinel octahedral-nanostructure material is taken as the negative electrode material of the lithium ion battery, the electrochemical performance is excellent.
Description
Technical field
The present invention relates to preparation method and the purposes of a kind of preparation method and purposes of transition metal spinelle, particularly a kind of titanium cobalt spinel.
Background technology
As a member in inorganic functional material field, transition metal spinel structure nano material because possessing the important characteristic such as dimensional effect, quantum effect, skin effect, at optics (Chem.Eur.J., 2007,13,746), magnetic (J.Am.Chem.Soc., 2008,130,13490), catalysis (Chem.Commun., 2009,1565), electrochemical energy storage (J.Mater.Chem.A, 2013,1,9024) etc. field has a wide range of applications.Because the particle diameter of material and appearance structure have a strong impact on for the physics of material, chemical property, therefore, autotelicly control synthesis will be carried out, to obtain the premium properties of expectation to material.
Inverse spinel structure cobalt titanate green (Co
2tiO
4) due to its good chemical stability, Chang Zuowei high-temperature resistant coating, inorganic pigment, in the last few years, it also result in the extensive concern of material scholar in the application in the fields such as magnetic.Traditional titanium cobalt spinel preparation method mainly adopts solid-phase synthesis, and reaction temperature is high, and the time is long, and the pattern of particle and size are all difficult to control, and cannot obtain regular morphology.But, there is not been reported for the preparation method of the titanium cobalt spinel that up to the present chemical constituent uniformity is good, purity is high, microstructure is regular, especially the titanium cobalt spinel material of special appearance, be also a blank so far, this constrains the further application of this material greatly.
Summary of the invention
The present invention seeks to provide a kind of raw material used to be easy to get, synthetic method is simple, the preparation method of the titanium cobalt spinel that operating procedure controllability is high and purposes.
The object of the present invention is achieved like this: the present invention is a kind of titanium cobalt spinel (Co
2tiO
4) nanometer octahedral structure material preparation method and used as lithium ion battery negative material, gentle liquid phase synthesis techniques is taked to prepare cobalt titanate nanostructure, technical parameter in regulation and control course of reaction, realize cheapness, the convenient chemical combination to titanium cobalt spinel nanometer octahedral structure material, and it should be used as lithium ion battery negative material;
Preparation method, it comprises the following steps:
(1) cobalt source is divalent cobalt, is selected from hydrated cobalt chloride (CoCl
26H
2o), oxalic acid hydrate cobalt (CoC
2o
42H O), acetate hydrate cobalt (C
4h
6o
4co4H
2or nitric hydrate cobalt (Co (NO O)
3)
26H
2o);
Titanium source is selected from titanium dioxide (TiO
2), butyl titanate (C
16h
36o
4or hydrated sulfuric acid titanium (Ti (SO Ti)
4)
29H
2o);
Titanium source is joined in the alkali lye of 0.5-2 mol/L and be mixed with solution 1; Cobalt source is joined mass ratio sugar adjuvant: in the solution of amine adjuvant=2:1, obtain solution 2.By solution 1 and solution 2 according to cobalt source and titanium source in molar ratio (1-5): 1 mixes and stirs;
(2) mixed material that step (1) obtains is moved in closed reactor under 100 ~ 250 DEG C of conditions, react and naturally cool to normal temperature after 8-40 hour and can obtain target product through separating-purifying.
In step (1), described base agent is one or more in NaOH, potassium hydroxide, lithium hydroxide; Described sugared adjuvant is one or more in fructose, glucose, sucrose, starch; Described amine adjuvant is one or more in hydroxylamine chloride, ammonium chloride, ammoniacal liquor.
Separating-purifying mode in described step (2) is centrifugal or Buchner funnel suction filtration, deionized water and absolute ethyl alcohol cyclic washing.
The preferred NaOH of alkali adjuvant in described step (1).
The preferred glucose of carbohydrate adjuvant in described step (1), the preferred hydroxylamine chloride of amine adjuvant.
Preferably, in step (1), cobalt source is hydrated cobalt chloride (CoCl
26H
2or acetate hydrate cobalt (C O)
4h
6o
4co4H
2o).
Preferably, in step (1), titanium source is titanium dioxide (TiO
2) or hydrated sulfuric acid titanium (Ti (SO
4)
29H
2o).
In described step (2), preferable reaction temperature is react 15-25 hour under 160-210 DEG C of condition, particularly preferably reacts 20 hours under 200 DEG C of conditions, and the titanium cobalt spinel nanometer of preparation high-purity regular appearance is octahedra.
The method that described titanium cobalt spinel nanometer octahedral structure material is used for the application of lithium ion battery negative material is:
(1) be by weight 70: 20: 10 ratio take that titanium cobalt spinel nanometer is octahedra respectively, acetylene black and Kynoar, then 1-METHYLPYRROLIDONE solution is added, abundant grinding or stirring 10 ~ 30min, the mixture of pasty state is coated on Copper Foil uniformly, dry at 100 ± 20 DEG C, afterwards the Copper Foil scribbling said mixture is rolled, cut obtained electrode slice;
(2) in the environment being full of argon gas, in conventional manner electrode slice, barrier film and lithium sheet be assembled into button cell and carry out constant current charge-discharge capacity and cycle performance test;
Result of the test: titanium cobalt spinel nanometer is octahedra under the current condition of 100 milliamperes/gram, first and second time discharge capacity be respectively 1320,750 MAhs/g, capacity tends towards stability thereafter; When elevated currents to 200 successively, 500,1000,2000,5000 milliamperes/gram, its capacity is respectively 600,550,500,420,220 MAhs/g; Under electric current returns to 100 milliamperes of/gram of conditions, its capacity still can return to 750 MAhs/g, and circulation 100 circle is unattenuated, fully shows high specific capacity and the high rate performance of excellence.
Beneficial effect: owing to have employed such scheme, prepared titanium cobalt spinel nanometer first octahedra, raw material used is easy to get, preparation method is simple, is easy to operation, and product be high-purity, domain size distribution is narrower, and the monocrystal of regular appearance, is comparatively easy to large-scale industrial production.Simultaneously, excellent chemical property is shown as lithium ion battery negative material using octahedra for this nanometer, both the shortcoming that commercial Li-ion battery conventional carbon negative material specific capacity is low had been overcome, possess again the excellent cycling stability that conventional transition metal oxide negative material does not possess, to exploitation new type lithium ion battery, there is directive function.
Advantage: raw material used is easy to get, synthetic method is simple, and operating procedure controllability is high, and products obtained therefrom is that purity is high, uniform particle diameter, is comparatively easy to expanding production.Meanwhile, this octahedron is used as lithium ion battery negative material and shows excellent chemical property.
accompanying drawing illustrates:
Fig. 1 is the embodiment of the present invention 1 titanium cobalt spinel nanometer octahedral powder X-ray diffraction pattern figure.
Fig. 2 is the octahedral transmission electron microscope photo of the embodiment of the present invention 1 titanium cobalt spinel nanometer.
Fig. 3 is the octahedral electron scanning micrograph of the embodiment of the present invention 1 titanium cobalt spinel nanometer.
Fig. 4 is the octahedral scanning transmission microphotograph of the embodiment of the present invention 1 titanium cobalt spinel nanometer and Co, Ti Element area profile photo.
Fig. 5 is the octahedral charge and discharge cycles figure of the embodiment of the present invention 1 titanium cobalt spinel nanometer.
Embodiment
The present invention is a kind of titanium cobalt spinel (Co
2tiO
4) nanometer octahedral structure material preparation method and used as lithium ion battery negative material, gentle liquid phase synthesis techniques is taked to prepare cobalt titanate nanostructure, technical parameter in regulation and control course of reaction, realize cheapness, the convenient chemical combination to titanium cobalt spinel nanometer octahedral structure material, and it should be used as lithium ion battery negative material;
Preparation method, it comprises the following steps:
(1) cobalt source is divalent cobalt, is selected from hydrated cobalt chloride (CoCl
26H
2o), oxalic acid hydrate cobalt (CoC
2o
42H O), acetate hydrate cobalt (C
4h
6o
4co4H
2or nitric hydrate cobalt (Co (NO O)
3)
26H
2o);
Titanium source is selected from titanium dioxide (TiO
2), butyl titanate (C
16h
36o
4or hydrated sulfuric acid titanium (Ti (SO Ti)
4)
29H
2o);
Titanium source is joined in the alkali lye of 0.5-2 mol/L and be mixed with solution 1; Cobalt source is joined mass ratio sugar adjuvant: in the solution of amine adjuvant=2:1, obtain solution 2.By solution 1 and solution 2 according to cobalt source and titanium source in molar ratio (1-5): 1 mixes and stirs;
(2) mixed material that step (1) obtains is moved in closed reactor under 100 ~ 250 DEG C of conditions, react and naturally cool to normal temperature after 8-40 hour and can obtain target product through separating-purifying again.
In step (1), described base agent is one or more in NaOH, potassium hydroxide, lithium hydroxide; Described sugared adjuvant is one or more in fructose, glucose, sucrose, starch; Described amine adjuvant is one or more in hydroxylamine chloride, ammonium chloride, ammoniacal liquor.
The preferred NaOH of alkali adjuvant in described step (1).
The preferred glucose of carbohydrate adjuvant in described step (1), the preferred hydroxylamine chloride of amine adjuvant.
Preferably, in step (1), cobalt source is hydrated cobalt chloride (CoCl
26H
2or acetate hydrate cobalt (C O)
4h
6o
4co4H
2o).
Preferably, in step (1), titanium source is titanium dioxide (TiO
2) or hydrated sulfuric acid titanium (Ti (SO
4)
29H
2o).
In described step (2), preferable reaction temperature is react 15-25 hour under 160-210 DEG C of condition, particularly preferably reacts 20 hours under 200 DEG C of conditions, and the titanium cobalt spinel nanometer of preparation high-purity regular appearance is octahedra.
The method that described titanium cobalt spinel nanometer octahedral structure material is used for the application of lithium ion battery negative material is:
(1) be by weight 70: 20: 10 ratio take that titanium cobalt spinel nanometer is octahedra respectively, acetylene black and Kynoar, then 1-METHYLPYRROLIDONE solution is added, abundant grinding or stirring 10 ~ 30min, the mixture of pasty state is coated on Copper Foil uniformly, dry at 100 ± 20 DEG C, afterwards the Copper Foil scribbling said mixture is rolled, cut obtained electrode slice;
(2) in the environment being full of argon gas, in conventional manner electrode slice, barrier film and lithium sheet be assembled into button cell and carry out constant current charge-discharge capacity and cycle performance test;
Result of the test: titanium cobalt spinel nanometer is octahedra under the current condition of 100 milliamperes/gram, first and second time discharge capacity be respectively 1320,750 MAhs/g, capacity tends towards stability thereafter; When elevated currents to 200 successively, 500,1000,2000,5000 milliamperes/gram, its capacity is respectively 600,550,500,420,220 MAhs/g; Under electric current returns to 100 milliamperes of/gram of conditions, its capacity still can return to 750 MAhs/g, and circulation 100 circle is unattenuated, fully shows high specific capacity and the high rate performance of excellence.
Embodiment 1:
the octahedral preparation of titanium cobalt spinel nanometer and structural characterization
Get 0.06gTiO
2put into container with 1.2gNaOH and add 30ml deionized water and be mixed with suspension-turbid liquid 1, get 0.3g hydrated cobalt chloride (CoCl
26H
2o), 0.1g glucose and 0.05g hydroxylamine chloride (H
3nOHCl) put into container and add 10ml distilled water and be mixed with solution 2; By suspension-turbid liquid 1 and solution 2 mixing and stirring and by mixing after material be transferred in closed pressure resistant reaction vessel, under 200 DEG C of conditions react 48 hours.Then be cooled to room temperature, open closed reaction vessel, and with Buchner funnel suction filtration, deionized water and absolute ethyl alcohol cyclic washing obtain dark green powder product.Product is accredited as Emission in Cubic titanium cobalt spinel Co through BrukerD8ADVANCEX ray powder diffractometer with CuK alpha ray (wavelength X=1.5418, scanning leg speed is 0.08 °/sec)
2tiO
4(Fig. 1), match with JCPDS card standard value No.39-1410, occur without other impurity peaks.
Fig. 1 is the octahedral powder X-ray diffraction pattern of titanium cobalt spinel nanometer; Wherein left ordinate is relative intensity (Intensity), and abscissa is angle of diffraction (2
θ).
Adopt the pattern of JEM1011 transmission electron microscope (voltage 100 kilovolts) and JSF-6700 scanning electron microscopic observation Emission in Cubic titanium cobalt spinel nano particle, as shown in Figure 2 and Figure 3, titanium cobalt spinel is distributed in the octahedra particle composition of nanometer of about 200nm primarily of grain size, size is even, and distribution of sizes is narrower.Analyzed can be obtained by EDSmapping, Co, Ti Elemental redistribution of product is even.
Fig. 4 is the octahedral scanning transmission microphotograph of the embodiment of the present invention 1 titanium cobalt spinel nanometer and Co, Ti Element area profile photo.
Electrochemical property test: be by weight 70: 20: 10 ratio take that titanium cobalt spinel nanometer is octahedra respectively, acetylene black and Kynoar, then 1-METHYLPYRROLIDONE solution is added, abundant grinding or stirring 10 ~ 30min, the mixture of pasty state is coated on Copper Foil uniformly, dry at 100 ± 20 DEG C, afterwards the Copper Foil scribbling said mixture is rolled, cut obtained electrode slice; In the glove box being full of argon gas, in conventional manner electrode slice, barrier film and lithium sheet be assembled into button cell and carry out constant current charge-discharge capacity and cycle performance test.Its chemical property as shown in Figure 5.
Embodiment 2: get 0.06gTiO
2put into container with 1.2gNaOH and add 30ml deionized water and be mixed with suspension-turbid liquid 1, get 0.31g acetate hydrate cobalt (C
4h
6o
4co4H
2o), 0.2g glucose and 0.1g hydroxylamine chloride (H
3nOHCl) put into container and add 10ml distilled water and be mixed with solution 2; By suspension-turbid liquid 1 and solution 2 mixing and stirring, the material after mixing is transferred in closed pressure resistant reaction vessel, reacts 48 hours under 180 DEG C of conditions.Then be cooled to room temperature, open closed reaction vessel, deionized water and absolute ethyl alcohol repeatedly centrifuge washing obtain dark green powder product.
Gained superfine powder is Emission in Cubic titanium cobalt spinel (JCPDSNo.39-1410), and crystallinity is good; The nanometer octahedron that product is about 170nm by average grain diameter forms.
Embodiment 3: get 0.1gTi (SO
4)
29H
2o puts into container and adds 30ml deionized water and is mixed with suspension-turbid liquid 1, gets 0.3g hydrated cobalt chloride (CoCl
26H
2o), 0.1g glucose and 0.1g hydroxylamine chloride (H
3nOHCl) put into container and add 10ml distilled water and be mixed with solution 2; By suspension-turbid liquid 1 and solution 2 mixing and stirring, then material is transferred in closed pressure resistant reaction vessel, reacts 32 hours under 200 DEG C of conditions.Then naturally cool to room temperature, open closed reaction vessel, deionized water and absolute ethyl alcohol repeatedly centrifuge washing, obtains dark green powder product.The powder obtained is through being characterized by Emission in Cubic Co
2tiO
4(JCPDSNo.39-1410), crystallinity is good; The nano particle being about 200nm by average grain diameter forms.
Claims (4)
1. a preparation method for titanium cobalt spinel, is characterized in that: the present invention is a kind of titanium cobalt spinel (Co
2tiO
4) nanometer octahedral structure material preparation method and used as lithium ion battery negative material, gentle liquid phase synthesis techniques is taked to prepare cobalt titanate nanostructure, technical parameter in regulation and control course of reaction, realize cheapness, the convenient chemical combination to titanium cobalt spinel nanometer octahedral structure material, and it should be used as lithium ion battery negative material;
Preparation method, it comprises the following steps:
(1) cobalt source is divalent cobalt, is selected from hydrated cobalt chloride (CoCl
26H
2o), oxalic acid hydrate cobalt (CoC
2o
42H O), acetate hydrate cobalt (C
4h
6o
4co4H
2or nitric hydrate cobalt (Co (NO O)
3)
26H
2o);
Titanium source is selected from titanium dioxide (TiO
2), butyl titanate (C
16h
36o
4or hydrated sulfuric acid titanium (Ti (SO Ti)
4)
29H
2o);
Titanium source is joined in the alkali lye of 0.5-2 mol/L and be mixed with solution 1; Cobalt source is joined mass ratio sugar adjuvant: in the solution of amine adjuvant=2:1, obtain solution 2;
By solution 1 and solution 2 according to cobalt source and titanium source in molar ratio (1-5): 1 mixes and stirs;
(2) mixed material that step (1) obtains is moved in closed reactor under 100 ~ 250 DEG C of conditions, react and naturally cool to normal temperature after 8-40 hour and can obtain target product through separating-purifying again.
2. the preparation method of a kind of titanium cobalt spinel according to claim 1, is characterized in that: in step (1), and described base agent is one or more in NaOH, potassium hydroxide, lithium hydroxide; Described sugared adjuvant is one or more in fructose, glucose, sucrose, starch; Described amine adjuvant is one or more in hydroxylamine chloride, ammonium chloride, ammoniacal liquor.
3. the preparation method of a kind of titanium cobalt spinel according to claim 1, is characterized in that: the separating-purifying mode in described step (2) is centrifugal or Buchner funnel suction filtration, deionized water and absolute ethyl alcohol cyclic washing.
4. the purposes of a kind of titanium cobalt spinel according to claim 1, is characterized in that: the method that described titanium cobalt spinel nanometer octahedral structure material is used for the application of lithium ion battery negative material is:
(1) be by weight 70: 20: 10 ratio take that titanium cobalt spinel nanometer is octahedra respectively, acetylene black and Kynoar, then 1-METHYLPYRROLIDONE solution is added, abundant grinding or stirring 10 ~ 30min, the mixture of pasty state is coated on Copper Foil uniformly, dry at 100 ± 20 DEG C, afterwards the Copper Foil scribbling said mixture is rolled, cut obtained electrode slice;
(2) in the environment being full of argon gas, in conventional manner electrode slice, barrier film and lithium sheet be assembled into button cell and carry out constant current charge-discharge capacity and cycle performance test;
Result of the test: titanium cobalt spinel nanometer is octahedra under the current condition of 100 milliamperes/gram, first and second time discharge capacity be respectively 1320,750 MAhs/g, capacity tends towards stability thereafter; When elevated currents to 200 successively, 500,1000,2000,5000 milliamperes/gram, its capacity is respectively 600,550,500,420,220 MAhs/g; Under electric current returns to 100 milliamperes of/gram of conditions, its capacity still can return to 750 MAhs/g, and circulation 100 circle is unattenuated, fully shows high specific capacity and the high rate performance of excellence.
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| CN106859659A (en) * | 2017-02-14 | 2017-06-20 | 西南政法大学 | The preparation of cobalt/aluminium compound blue nanometer powder and its finger mark process for show |
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Address after: 221116 No. 1 University Road, copper mountain, Jiangsu, Xuzhou Patentee after: CHINA University OF MINING AND TECHNOLOGY Address before: 221116 Research Institute, China University of Mining and Technology, Xuzhou University, Jiangsu, China, Patentee before: CHINA University OF MINING AND TECHNOLOGY |
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